Textile treating composition comprising a mixture of a urea-formaldehyde condensate and a triazone-formaldehyde condensate



June 1967 GEORGE SHIU YIM POON 3,324,062

TEXTILE TREATING COMPOSITION COMPRISING A MIXTURE OF A UREA-FORMALDEHYDECONDENSATEIAND A TRIAZONE-FORMALDEHYDE CONDENSATE Filed June 25, 1957 4Sheets-Sheetl EFFECT OF DEPRESSANT ON ACROLEIN MODIFIED UREAFORMALDEHYDE TREATED FABRIC 6G CURED A'T l30 c.

wrrnou'r DEPRESSANT 1 PERCENT 1.055 m STRENGTH. our: TO CHLORINERETENTION 0zen;ssm-r ADDED TO GIVE A CONSTANT TOTAL CONCENTRATION OFI596 1! 0 9 l2 I5 1 PERCENT ACROLEIN moumzp UREA FORMALDEHYDE J=l.

EFFECT OF DEPRESSAN'I' ON ACROLEIN MODIFIED UREA FORMALDE HYDE TREATEDFABRIC 8 CURE!) AT I50C.

/ WITHOUT ospaessm-r PERCENT LOSS m STRENGTH our: TO CHLORINE RETENTIONI /r A DEPRESSANT ADDED TO cm: A

coNs'rAN'r TOTAL CONCENTRATION 0F|59a I! Ii I 12 I5 PERCENT ACROLEINMODIFIED UREA FORMALDEHYDE L lNVENTOR GEORGE SH/U VIM POON ATTORNEYSJ1me 1957 GEORGE sI-IIu YIM POON 3,3

TEXTILE TREATING COMPOSITION COMPRISING A MIXTURE OF A UREA-FORMALDEHYDECONDENSATE AND A i TRIAZONE-FORMALDE'HYDE CONDENSATE Filed June 25, 19574 Sheets-Sheet 2 EFFEC OF DEPRESSANT ON ACROLEIN MODIFIED UREAFORMALDEHYDE TREATED FABRIC 0 6c .CURED AT I70 0.

r WIT'HOU'T DEPREssANT PERCENT LOSS IN STRENGTH 7 DuE To CHLORJNERETENTION DEPREssANT ADDED m cm A CONSTANT ToTAI. coI -4cENTRATIoN OFI594 I l I .I I6 I: I: I5 PERCENT ACRDLEIN MODIFIED UREA FORMALDEHYDE.1.=:.&

EFFECT OF OEPFLESSANT ON DIMETHYLOL UREA 0c TREATED FABRIC CURED ATwITI-IouT DEPRESSANT e0 l /I so PERCENT L055 IN STRENGTH DuE To CHLORINERETENTION l 4 DEPaEssANT ADDED TO GIVE A CONSTANT TOTAL CONCENTRATION OF[5% o o J I I I2 I5 PERCENT DIMETHYLOL UREA INVENTOR 4:2.4- GEORGE SH/UVIM POON ATTORNEYS June 1967 GEORGE SHIU YlM POCJN 3,3 ,062

TEXTILE TREATING COMPOSITION COMPRISING A MIXTURE OF UREA-FORMALDEHYDECONDENSATE AND A TRIAZONE-FORMALDEHYDE CONDENSATE Filed June 25, 1957 4Sheets-Sheet 5 EFFECT OF DEPRESSANT ON DIMETHYLOL UREA l0 TREATED FABRICCUFLED AT J I I DE PRESSANT 8O FE RC ENT LOSS IN STRENGTH DUE TOCHLORINE RETENTION DEPRESSAN ADDED TO GIVE A CONSTANT TOTALCONCENTRATION OF I59,

DUE TO CHLORINE RETENTION PERCENT 9 DIMETHYLOL UREA METHYLOL UREA LIIDEFRESSANT ADDED TO GIVE A CONSTANT TOTAL CONCENTRATION OF I591,

3 6 PERCENT DIMETHYLOL UREA INVEN TOR GEORGE SH/U VIM POO/V ATTORNEYSJune 6, 1967 TEXTILE TREATIN Filed June 25, 1957 PERCENT L055 INSTRENGTH ouz TO CHLORJNE RETENTION EFFECT OF DEPRESSANT ON DIM TREATEDFABRIC CU EORGE SHIU YIM POON G COMPOSITION COMPRI UREA FORMALDEHYDECONDE TR IAZONE-FORMALDEHYDE SING A MIXTURE OF A NSATE AND A CONDENSATE4 Sheets-Sheet 4.

ETHYLOL ETHYLENE UREA RED AT I50C.

WITHOUT DEPRESSANT CONCEA DEPRESSANT ADDED CONSTANT TOTAL C TRATION OFI596 TO GIVE A IOG EFFECT OF DEPRESSANT O TREATE D FAB J PERCENTDIMETHYLOL ETHYLENE UREA N TETRAMETH FUC CURED AT YLOL ACETYLENE DIUREAWITHOUT DEPRESSANT PERCENT LOSS IN STRENGTH DUE TO CHLORJNE RETENTIONDEPRESSANT ADDED TO GlVE AOCONSTANT TOTAL C NCENTRATIO J i la PERCENTTETRAMETHYLOL ACETYLENE DIUREA INVENTOR GEORGE SH/U VIM POON ATTORNEYSUnited States Patent TEXTHLE TREATING CGMPOSITION COMPRISING A MIXTUREOF A UREA-FORMALDEHYDE CON- DENSEATE AND A TRlAZONE-FORMALDEHYDECONDENSATE George Shin Yim Poon, Danville, Va., assignor to Dan RiverMills, incorporated, Danville, Va., a corporation of Virginia Filed June25, 1957, Ser. No. 667,824 27 Claims. (Cl. 260-2944) This application isa continuation-in-part of the following applications: S.N. 584,443 filedMay 14, 1956, SN. 632,434 filed January 4, 1957 and S.N. 655,956 filedApril 30, 1957 all now abandoned.

This invention relates to the production of wrinkle-resistant cottontextile fabric. More specifically, it relates to an improved method ofproducing such fabrics and to improved compositions for use in suchmethods.

An important object of this invention is an improvement of theproperties of wrinkle-resistant cotton fabrics, particularly withrespect to chlorine retention. Another important object of the inventionis the broadening of range of treating conditions which may be employedto produce the desired fabrics and thereby providing means forfacilitating production of wrinkle-resistant fabrics possessingexceptionally desirable properties. Another object of the invention isthe production of cotton fabrics having a high degree of resistance towrinkling and a high resistance to damage from retained chlorinethroughout the normal life of the fabric.

These and other objects of the invention are accomplished generally bytreating cotton fabrics in accordance with conventional manipulativeprocedures for achieving wrinkle-resistance using novel and newimpregnating compositions which produce unexpected advantages in severaldirections, particularly in the area of depressing the damage resultingfrom retained chlorine.

COEFFICIENT OF CHLORINE DAMAGE It has been found that, within practicalworking limits, the degree of damage from retained chlorine is afunction of the particular resin being used and not of the amount ofresin being used. This means that, for any given resin, low solids onthe fabric will be just as damaging as high.

Thus, it may be stated that each resin has a coeflicient of chlorinedamage. The art of testing materials is not sufficiently developed toassign absolute values to these coefficients, but it is safe to say thatthe more commonly used resins have a coefficient of chlorine damage wellabove the desired limit, and arbitrary values based on present testingmethods may be assigned with reasonable relative accuracy.

For purposes of this invention, the coefficient of chlorine damage forany given material may be expressed as the percentage of strength losswhen tested by the AATCC test method 6952, of an 80 square cotton fabricmade wrinkle-resistant by being impregnated with that material and 1% of23% 'monoethanolamine hydrochloride, dried and cured at 150 C. for 70seconds. By this test, the coefficient of chlorine damage for severalknown materials may be expressed thus:

Tetramethylol acetylene diurea 100 Dimethylol urea 85 Urea acroleinformaldehyde 6O Dimethylol ethylene urea 50 It will be understood thatthese figures are somewhat arbitrary in that the testing procedure usedfor measuring the damage from retained chlorine is not alwaysreproducible from one laboratory to another laboratory. However, it hasbeen established through a long period of 3,324,062 Patented June 6,1967 ice testing that the relative values are reliable as long as thecoefficient of chlorine retention is below 100. It will be realized thatthe figures represent an actual measurement of the percentage ofstrength loss and represents a tot-a1 strength loss which may berelatively less than it should be in relation to a resin shown as 60 or85.

HIGHLY CHLORINE RETENTIVE MATERIALS The highly chlorine retentivematerials used as one component of this invention may be defined asthose Water soluble, thermosetting-resin forming, materials, which, whencured on cellulose fabrics, will produce a substantially higher degreeof wrinkle resistance than that produced by the same unit quantity ofthe depressant as defined below, which contains a plurality of reactivenitrogen groups reacted with formaldehyde, and which has a coefficientof chlorine retention as defined above at least as high as that ofdimethylol ethylene urea.

Urea formaldehyde is probably the most important of these materialsbecause it is inexpensive and it produces a high degree of wrinkleresistance per unit quantity. Urea formaldehyde is most commonly used inthe form of dimethylol urea, but there are many other closely relatedurea formaldehydes which fall within the scope of this invention. Alsowithin the scope of this invention are the following specific compounds:

tetramethylol acetylene diurea acrolein modified urea formaldehydethiourea formaldehyde dimethylol ethylene urea dicyandiamideformaldehyde DEPRESSANT hyde. These same depressants may also be definedin terms of their method of manufacture. They may be prepared by thereaction of a dimethylol urea. with a primary amine and an appropriateamount of formaldehyde. A mono-amine produces one triazone ring and adiamine produces two triazone rings in a single molecule.

These same depressants may also be defined in terms of the followingstructural formula:

wherein R is selected from the group consisting of hydrogen, methyloland methoxymethyl; R is selected from the group consisting of hydrogenand an alkyl group having no more than three carbon atoms; R is selectedfrom the group consisting of hydrogen, an alkyl group having from 1 to 4carbon atoms, an alkanol group having from 1 to 4 carbon atoms and analiphatic group having from 2 to 6 carbon atoms and being connected atits opposite end to the 5 position of a tetrahydro-2(1)-s-triazone groupfalling within this definition; and R is selected from the groupconsisting of hydrogen, methylol, methoxymethyl, an alkyl group havingfrom 1 to 4 carbon atoms and an aliphatic group having from 2 to 6carbon atoms and being linked at its opposite end with the 3 position ofa tetrahydro-2(l)-s-triazone group falling within this definition andwherein the compound contains at least one group selected from the groupof methylol and methoxymethyl.

The term triazone formaldehyde has been employed throughout thespecification and claims as a simple term to designate the productsincluded in the structural formula just defined and as further explainedin the two preceding and the two following paragraphs.

These triazones are well known compounds. The triazones, per se, aredescribed, for example, in Patent No. 2,016,521, issued in 1935 toSteindorfif and Paquin. Some of the triazone formaldehydes of thisinvention are disclosed in Martone Patent 2,641,584 of .1953. Thecorresponding formaldehyde derivatives of thiotriazones do not functionsatisfactorily in the process of this invention.

Thus, the three sub-species of triazone formaldehyde in this inventionare defined by the following empirical formulas:

A mono triazone A bis triazone with a. 1,3 aliphatic linkage II ll O Abis triazone with a 5,5 aliphatic linkage I I I I N-CH CHN Certainadvantages may be realized by using as the depressant1,3-dimethylOl-S-ethyI-tetrahydro 2(1)-s triazone and much of the scopeof this invention has been determined in terms of tests made with thatproduct.

GENERAL DESCRIPTION The conventional procedure for producing wrinkleresistant fabrics is to impregnate the fabric with an aqueous solutioncontaining an acid catalyst and a resin forming material after which theimpregnated fabric is heated to dry the fabric and cure the resin. Themost difficult problem in this process has been that the processes whichproduce high wrinkle resistance also produce high damage from retainedchlorine, commonly referred to as the problem of chlorine retention.

Numerous suggestions have been made for eliminating chlorine retention.Some of these ideas have been meritorious and others have met withfailure and yet even the most meritorious ones have not been entirelysatisfactory.

The gist of this invention is the improvement of the conventionalprocess of making textile fabrics wrinkle resistant by using at leasttwo components in combination as the material for effecting wrinkleresistance. One component is a resin forming material which produceshigh wrinkle resistance but which also has a high coefiicient ofchlorine retention. The other component is a chlorine damage depressantwhich has just been defined and which is also a resin forming material,but one which produces a relatively low degree of wrinkle resistance.The primary advantage of the invention is the securing of cellulosefabrics having high wrinkle resistance and low damage from retainedchlorine retention.

An especially advantageous feature of this invention is thatimpregnating solutions containing triazone formaldehyde depressant maybe applied by conventional procedures and the process remains responsiveto other procedures for reducing chlorine retention damage, therebyenabling assurance of elimination of damage from retained chlorine.

The triazone formaldehydes of this invention also produce some wrinkleresistance and therefore are especially suited for this depressantpurpose.

The important fact of this invention is not that these triazoneformaldehydes are resistant to damage from retained chlorine, but thatthey also have the unexpected property of strongly depressing thecoefficient of chlorine damage of other less expensive resin-formingmaterials.

Those resin-forming materials which have a lower coefficient of chlorinedamage are easily converted to a safe coefficient of chlorine damagewhile those normally possessing a higher coefiicient of chlorine damageare more difficult to master and they require a much larger amount oftriazone formaldehyde to accomplish the desired result.

Another outstanding advantage of the triazone formaldehydes is theirability to maintain the depression of the coefiicient of chlorine damageof resin treated fabrics on subsequent laundering. Fabrics treated inaccordance with many prior procedures for obtaining resistance to damagefrom retained chlorine will produce satisfactory results on initialtests, but after 5-l0 commercial launderings will show a markedreduction of their resistance to this damage so that the splendidresults which were initially obtained will be absent in the later stagesof normal fabric usage. However, fabrics treated in accordance with thepresent invention retain their resistance to damage from retainedchlorine even after repeated commercial launderings, thus protecting thefabric during its normal, useful life.

Other important features of this invention include new methods ofmanufacturing particular chemical products useful in fabric treatment aswell as the chemical products themselves. These feat-ures are consideredseparately below.

FABRIC PROCESSING This invention has its greatest value in the treamentof cotton fabrics where the sensitivity of the fabric to a hard curemakes the problem of eliminating damage from retained chlorine a severeone. At the same time, the beneficial results of the invention may alsobe realized in the treatment of other cellulose fibers such as rayon andlinen.

Obviously, the preferred way of carrying out the invention is toimpregnate the fabric with a single solution containing the twocomponents of the invention, namely a depressant resin forming materialand a resin forming material which has both a high wrinkle resistancevalue and a high coeflicient of damage from retained chlorine. However,it has been found that the advantages of the invention may still berealized if the fabric is first treated according to conventionalprocedure with first one of the components and later run through thesame steps using only the other component as the resin forming material.The sequence in which the two materials are used appears to beimmaterial.

In carrying out the present invention one may refer to the prior art fordetermination of the exact nature of the generally old processing steps.For example, it is conventional to apply resin forming materials totextile fabrics from aqueous solutions and such technique is used inthis invention. It is conventional to use an acid catalyst. The range ofsatisfactory catalysts is well known. Among the satisfactory ones arezinc nitrate, calcium chloride, tartaric acid, monoethanolaminehydrochloride, 2-ethyl-2- amino-propanol-l-hydrochloride, magnesiumchloride,

mixtures of these compounds and many others. Naturally some of thesecatalysts are better than others in specific applications of theinvention, but in general, any of the known catalysts may be usedsuccessfully in the practice of this invention.

In the impregnation step, there has been considerable variation in priorart processing in that the fabrics being treated have been impregnatedwith from 50% to 150% of their weight of the aqueous treating solution.Such a range is entirely within the scope of this invention. How ever,as a practical matter it has been found desirable to impregnate thefabric with from about 65% to 75% of its weight of solution. In the stepof heating the fabric to dry the fabric and cure the resin, there arealso known variations. Some prefer to have a separate drying stepfollowed by a curing step. Others combine the steps. This invention issusceptible of either mode of operation. The time and temperature ofthese steps are likewise the subject of much variation from plant toplant and often even within the same plant. In most plants, the time oftreatment is arbitrarily fixed in accordance with the capabilities ofthe particular equipment being used and then the temperature of the cureis varied to achieve the desired degree of curing. These curingtemperatures may vary anywhere from 120' C. to 200 C. and the time mayvary from one minute to five minutes. It is well known that damage fromretained chlorine is reduced by a hard cure, that is, that the longerthe time and the higher the temperature of the cure, the lower thedamage that will be caused by retained chlorine in wrinkle resistantfabrics. This is, of course, limited by the fact that a hard cure alsodegrades fabric. Thus, in the practice of the present invention it wouldappear desirable to use a relatively hard cure, but the advantages ofthe invention may be realized throughout the range of normal curingconditions. Sometimes the advantages of the invention are moststrikingly revealed in operations at the lower temperatures. This is ofextreme importance to production because this invention enables thecuring conditions to be so regulated as to materially reduce thetendency to overcure and degrade fabrics. In other words, highproduction with low seconds may be directly attributable to thisinvention.

Still another variable is the amount of resin forming material depositedon the fabric. Some fabrics are treated to make them merely wrinkleresistant so that wrinkles will hang out of the fabrics overnight. Otherfabrics are treated to produce the so-called wash and wear effect. Inthe latter case, the amount of resin forming material is much higherthan in the former. In the latter case it is also common to use any of alarge number of additives, such as thermoplastic resin emulsions, waterrepellents, softeners, lubricants and the like. This invention may bevery successfully used in either of the above applications. In someinstances, the amount of resin forming materials may be as low as 5% andin other instances it may be as high as 40%.

Yet another variable in the field is the quantity of catalyst to beused. Some base the quantity of catalyst on the amount of resin andothers base it on the amount of fabric or the nature of the fabric. Analkaline fabric will require more catalyst than a neutral fabric. It isan outstanding feature of this invention that its benefits andadvantages may be realized over an extremely wide range of catalystconcentrations. Ordinarily the amount of catalyst will be in the natureof from about 0.5% to 3% based on the total weight of the solution.

RATIO OF DEPRESSANT TO HIGHLY CHLORINE RETENTIVE MATERIAL There are noclearly defined limits which may be used to express the exact ratio ofthe resin forming components of this invention. The problem is somewhatcomplicated by the fact that there are no established standards of whatis and what is not a commercially satisfactory level of damage fromretained chlorine. It will be apparent that even minute quantities ofthe triazone formaldehydes of this invention do have a beneficial effectin the lowering of the damage from retained chlorine of the resinforming materials having a high coefficient of chlorine damage. By thesame token, it will also be realized that there are no establishedstandards of wrinkle resistance. This is especially a problem with theadvent of wash and wear fabrics. However, it is well established thatevery textile finisher is seeking the highest possible wrinkleresistance he can economically obtain without placing goods on themarket in such condition that they are apt to be returned because offabric degradation. Thus, as a practical matter, each user of thepresent invention will want to regulate the ratio of the components ofthis invention to enable use of the largest possible relative amount ofthe resin forming component having a high wrinkle resistance valuewithout risking fabric damage from retained chlorine below what isconsidered to be a safe level. It appears that a molar ratio ofcomponents in the nature of from about 1:10 to 10:1, respectively,defines the area of most desirable operation in accordance with theinvention. It will be understood that this mol ratio is based on amonotriazone as distinguished from the his triazones which aretheoretically twice as effective.

The molar ratio of 1:10 to 10:1 merely defines the broader limits of theinvention and in practice, the actual ratio of compounds will beregulated within that range in accordance with the specific triazoneformaldehyde used, the specific highly chlorine retentive material usedand the arbitrarily established values being sought.

It has been found that the purity of the triazone has a definiterelationship to its value as a depressant. Some of the triazones are notproduced in anything like the theoretical quantities and yet they may besatisfactorily used in the impure state because it is cheaper to use anexcessive quantity of the impure product than to practice the processesrequired for purification.

To illustrate the variations in satisfactory molar ratios, an impure 1,3-dimethylol-S-ethyl-tetrahydro-Z(l)-s-triazone was prepared by heatingone mole of dimethylol urea with one mol of ethylamine under alkalineaqueous conditions for about two hours and this product was thereafterreacted with two mols of formaldehyde as formalin and adjusted to aboutpH 5.5. Theoretically, this product contained one mol of triazoneformaldehyde, This product was then used in varying quantities withdimethylol urea, dimethylol ethylene urea, *acrolein modified ureaformaldehyde and tetramethylol acetylene diurea for the purpose ofestablishing the relative molar quantities required to be used indepositing 8% SOlids on a cotton fabric while retaining what isarbitrarily considered a safe level of damage from retained chlorine.Under these conditions, it was found that the minimum amount of triazoneformaldehyde for each mol of resin was as follows:

Mols

Dimethylol urea 1.0 Dimethylol ethylene urea 0.1 Acrolein modified ureaformaldehyde 0.5 Tetramethylol acetylene diurea 2.0

In contrast to these results, a mixture of dimethylol urea and1,3-dimethylol-5 ethyl-tetrahydro-2(1)-s-triazone was prepared byreacting less than a stoichiometric amount of ethylamine with dimethylolurea under aqueous alkaline conditions and thereafter adding thetheoretical amount of formaldehyde required to methylolate the newlyformed triazone. Apparently this product resulted in a triazone ofhigher purity because a variation of the theoretical mol ratios of thetriazone formaldehyde and unreacted dimethylol urea resulted in afinding that only 0.3 mol of triazone formaldehyde was required for eachmol of dimethylol urea to produce the same satisfactory degree of damagefrom retained chlorine as in the previously listed illustrations.

The upper limit of 10 mols of triazone for each mol of resin is somewhatarbitrarily established, but it is believed that the most practicalrange of operation is with a maximum safe amount of the highly chlorineretentive material which produces a higher wrinkle resistance value.

Thus, it will be seen that the broader aspects of this invention havebeen described in terms of the means which may be used to depress thechlorine damage of wrinkle resistant fabrics and the products used inconnection therewith.

There are also modifications or other aspects of the invention which arealso important.

PRE-POLYMERIZED RESIN One such aspect of the invention relates to themanufacture of wrinkle resistant textile fabrics characterized by arelatively stiff hand or feel. It also relates to prepolymerized ureaformaldehyde type resin forming materials which are water soluble andsuitable for application to textile fabrics to impart stiffness and bodywhile producing wrinkle resistance and dimensional stability. Such resinforming products may be used on cotton and rayon fabrics, as well as onnylon, acetate and other woven and knit textile fabrics.

A great disadvantage of the water soluble prepolymerized ureaformaldehyde type resin forming materials which have heretofore beenused for these purposes is their limited stability. Another distinctdisadvantage of these materials is that on application to cellulosicfabrics, and particularly cotton fabrics, they retain chlorine whichoften damages the strength of the fabric on subsequent processing,particularly in chlorine bleaching.

One object of this aspect of the invention is the provision of a highlystable, water soluble, partially prepolymerized, urea formaldehyde typeresin. Another object of this part of the invention is the provision ofstiffened cellulosic fabrics having an excellent wrinkle resistance anddimensional stability which are retained even after commercial whitewashing. Still another object of this part of the invention is theprovision of a cellulosic textile fabric having the aforementionedcharacteristics and at the same time having a high degree of resistanceto chlorine yellowing and damage from retained chlorine which are alsoretained on commercial white Washing. It is also an object of this partof the invention to provide means for adjusting the stiffness of textilefabrics and it is still .a further object of the invention to accomplishthe above-named objectives by a process of extreme simplicity, usingmaterials of an inexpensive nature.

The advantages of that aspect of the invention described above areincorporated and preserved in the practice of this aspect of theinvention. However, the gist of this part of the invention is thediscovery that the combination of the triazone formaldehydes with ureaformaldehyde may be pic-polymerized to produce stiffening agents ofunexpected stability. It is also considered an important part that thisadded stability and stiffness can be attained without sacrificing theother benefits of my prior invention.

Generally, the objects of this part of the invention are accomplished bythe preparation of a mixture of urea formaldehyde and a triazoneformaldehyde which is then reacted by heating for a predetermined timeat a predetermined temperature on the acid side, thereafter applying thethus formed product to a textile fabric from a water solution,preferably containing an acidic catalyst, after which the fabric isheated to effect drying and to cure the resin.

The formation of the mixture of the urea formaldehyde and the triazoneformaldehyde may be effected in any of a number of ways. In someinstances, the previously formed triazone formaldehyde and ureaformaldehyde may be mixed together in the desired proportions or inother instances one may first form a triazone formaldehyde andthereafter add urea and formaldehyde separately. Still another techniquefor some triazone formaldehydes is to first add the desired amount ofurea formaldehyde and add an amount of a primary lower alkyl aminesufficient to produce the desired mol ratio of urea formaldehyde andtriazone formaldehyde. In any of these events, the desired mixture issubsequently heated and finished off on the acid side.

Still another and the preferred method of producing the pre-polymerizedfabric treating product of this invention is to react a primary aminesuch as monoethylamine with urea and an urea formaldehyde concentrate inone portion, after which a second portion of urea formaldehydeconcentrate and urea are added to the first portion (the ureaformaldehyde concentrate contains an excess of formaldehyde and has aratio of 60% formaldehyde to 25% urea and the balance water). This willproduce a mixture of dimethylol urea and 1,3-dimethylol-5ethyl-tetrahydro-ZU)-s-triazone. As in the prior instance, the mixtureof urea formaldehyde and triazone formaldehyde will polymerize on theacid side.

It will be understood that the stiffening properties of the finalproduct will necessarily be a function of the time and temperature ofthe pre-polymerization, as well as the pH at which the reaction iscarried out and the mol ratio of the urea formaldehyde to the triazoneformaldehyde.

The number of. variables which must be taken into account in carryingout stiffening in that part of the present invention are quite high andthe permissive range of any one variable is dependent upon theconditions chosen for the other variables. For this reason it is almostimpossible to set a specific pH range, a time range, or a temperaturerange. Further complicating the picture 15 the fact that the specificend use of the pre-polymerized resin product will require difierentconditions.

However, by arbitrarily choosing standard conditions for certain of thevariables and varying one condition, such as time, one skilled in theart may readily obtain a Wide range of products having all thebeneficial properties of this invention.

Despite the difiiculties attendant to the presentation of numericalvalues for the permissive ranges of the variable conditions, there arecertain known relationships which may be used as guiding principles toenable one skilled n the art to accomplish the objectives of thisinvention in a large number of ways.

For example, for any given degree of polymerization and any given molratio of reactants, the shorter the time of condensation, the lower thepH and/ or the higher the temperature required. Or, stated another Way,the higher the pH, the longer the time and/or the higher the temperaturerequired. Or, stated still another way, the lower the temperature, thelonger the time and/or the lower the pH required. If one desires toincrease the stiffening properties of the resin being produced this canbe done by increasing the time or increasing the temperature of loweringthe pH of the reaction.

The end product may also be varied by varying the mol ratio of thereactants, and the greater the amount of urea formaldehyde in relationto triazone formaldehyde the more stiffening will be obtained. However,if the amount of urea formaldehyde is increased, less strenuousconditions of pH, time and temperature are required for the same degreeof polymerization.

Actually the permissive ranges of the reaction conditions and mol ratiospermitted by the scope of the present invention can be varied to highlyimpractical limits. For example, it is theoretically possible to varythe time of reaction from an instantaneous time to an almost infinitetime. Of course, as a practical matter, one would choose a relativelyshort time, say from 15 minutes to two hours. Similarly, the temperatureof the reaction could theoretically be anywhere from room temperature tothe boiling point of the reaction mixture but, again,

as a practical matter, the reaction temperature should be a moderate oneto enable maximum flexibility and control.

The pH of the mixture during pre-polyrnerization may be extended overalmost the entire range of acidity, provided the other conditions aresuitably modified. Yet as a practical matter, the pI-l should be in amedian range, preferably standardized to permit the end product to bevaried by such easily controlled conditions as time and temperature.

There does not appear to be any sharp break point defining the limits ofthe mol ratios of reactants which may be used to obtain the benefits ofthis invention. If one chooses to obtain all the benefits of the broaderaspects of this invention, the limits defined in the earlier portion ofthis application should be followed. However, for purposes of obtainingonly the stability improvements of the stiffening part of thisinvention, it appears that there is a direct proportion between theamount of triazone used (based on the number of triazone nuclei) and thestability of the product.

The stability problem solved by this invention is really a dual problem.If the degree of polymerization of the product is too great, thesolubility of the product is reduced, because if polymerization iscarried to its extreme limits, the product will set up into a solidmass. On the other hand, if the degree of polymerization is too small, awater-soluble precipitate will form. The range of products intended tobe covered by this invention is the entire range between the polymerizedproducts which will be water-insoluble and the range of partiallypolymerized products which are subject to the formation of awatersoluble precipitate.

SPECIAL UREA FORMALDEHYDE-TRIAZONE FORMALDEHYDE PREPARATION In onepreferred modification, useful only where a urea formaldehyde is one ofthe highly chlorine retentive materials, especially beneficial resultsare obtained by preparing the triazone formaldehyde by the reaction ofeither dimethylol urea or an appropriate quantity of formaldehyde andurea with less than an equimolar quantity of primary amine groups. Theadvantage of this process is that its product produces a higher wrinkleresistance per unit quantity when applied to cellulose fabric with lessdamage from retained chlorine. It is believed that the reason for theadvantage is that a triazone of high purity is obtained. Quantitativetests against triazone formaldehydes prepared from 100% pure triazonessupport this view.

The depressant effects on several resins have been established bycareful test examples as will be apparent from the following.

DEPRESSANT EFFECTS ON ACROLEIN-UREA-FORMALDEHYDE The resin-formingmaterial used in this series oftest examples was a condensation productof acrolein, urea and formaldehyde prepared generally in accordance withthe procedure of US. Patent 2,600,780 issued to Franz Kohler June 17,1952 by using the following ingredients:

Parts Formaldehyde (37%) 1525 Urea 425 Water 220 Acrolein 150 Glacialacetic acid 4 A series of fabric samples 37 inches long and 8 incheswide were cut from asingle bleached, mercerized, scoured and dried pieceof plain woven cotton check running about 4.5 yards per pound. Thesesamples were divided into three equal groups, A, B and C, for testingthe effects of the depressant at three separate curing temperatures,namely, A170 C., Bl50 C. and C130 C.

Each group A, B and C contained 20 samples, divided into two equalsubgroups of 10. The first subgroup (1) of each of the groups A, B and Cwas impregnated with varying amounts of acrolein-urea-formaldehyde. Thesecond subgroup (2) of each was impregnated withacrolein-urea-forrnaldehyde in the same varying amounts, but acommercial 1,3-dimethylol-5-ethyl-tetrahydro-2(1)-s triazone, adepressant, was added to each sample in an amount sufiicient to bringthe total solids of the impregnating solution to a constant solidscontent equivalent to 15% of a solution of acrolein-urea-formaldehyde.

Each dry sample was individually impregnated with about 65% of its ownweight of an aqueous solution containing its specified concentration ofresin-forming materials with or without depressant and furthercontaining 0.5% monoethanolamine hydrochloride catalyst. The impregnatedsamples were air dried and subsequently cured at the respectivetemperatures of groups A, B and C.

These treated samples were washed, centrifuged, pressed, conditioned andthen tested at standard conditions to determine the wrinkle resistance,strength properties and chlorine damage as measured by the AATCCTentative Test Method 6952, Damage Caused by Retained Chlorine.

The wrinkle resistance of all samples in groups A(2), B(2) and C(2) wassatisfactory. There was, however, a definite distinction between thewrinkle resistances of the A, B and C groups as would be expected inview of the well-known fact that higher curing temperatures producehigher measurements of wrinkle resistance.

The Wrinkle resistance of the A(1), 13(1) and C(1) groups was entirelysatisfactory at the normal concentrations of resin-forming materials,but naturally fell off in the lower and impractical concentrations.

The'strength properties of the treated samples were all consideredsatisfactory.

The unexpected effect of the depressant is graphically illustrated ingraphs 1, 2 and 3.

DEPRESSANT EFFECTS ON DIMETHYLOL UREA The experimental procedure of thetests used on acrolein-urea-formaldehyde were repeated without changeexcept for the substitution of dimethylol urea as the resinformingmaterial. The test results generally duplicated the pattern of theprevious series as to wrinkle resistance and strength properties. Thedepressant effects are illustrated graphically in graphs 4, 5 and 6.

Other depressants and other resin-forming materials have not been sothoroughly investigated, but the repetition of the pattern of depressanteffects have been clearly demonstrated by following the B group of theexperimental example outlined above for dimethylol ethylene urea andtetramethylol acetylene diurea with the results illustrated in graphs 7and 8.

It will be noted that the resistance to damage caused by retainedchlorine is not always completely eliminated in some of the tests,particularly when using such highly chlorine retentive materials astetramethylol acetylene diurea. However, it is clearly shown that thecoefficient of chlorine damage of each resin is greatly depressed by thetriazone formaldehydes of this invention. Thus, it will be clear thatthe gist of this invention is the depressing of the coefiicient ofchlorine damage of those resins which are subject to this difliculty.

It is believed that those skilled in the art will have no difliculty incarrying out this invention on the basis of the examples and graphspresented above, but the following typical examples illustrate prefenredprocedures for carrying out the invention.

Example I 51.9 pounds of dry urea were added with stirring to 1059pounds of a urea formaldehyde concentrate containing 25% urea andformaldehyde in water. To this, 290 pounds ofa monoethylamine solution(71% solution in water) was added slowly with cooling to keep thetemperature below 140 F. After the addition was complete, reaction wascontinued for about two hours at 155 F. and the pH was adjusted to pH5.5-6.0 after which the temperature was raised to 160 F. for 1 /2 hours.This product was cooled to 120 F. and the pH was adjusted to pH 4.4-4.8.This second heating stage was used to stabilize the product and assureuniformity of results.

This final product was a mixture of dimethylol urea and1,3-dimethylol-S-ethyl-tetrahydro 2(1)-s-triazone in a molar ratio about1:6.3 respectively, with a slight excess of formaldehyde.

An aqueous solution of 12% of this product (about 70% solids) and 1 /4%of a 50% solution of monoethanolamine hydrochloride was prepared and aplain woven, bleached, mercerized and soured 100% cotton gingham runningabout 4 /2 yards per pound was impregnated with about 65% of its ownweight of this solution. The impregnated fabric was dried at 200 F. andcured at 300 F. for 70 seconds.

The chlorine retention damage of the fabric which would be expected tobe high because of the urea formaldehyde, was tested and found to beabout equal to an untreated fabric. The wrinkle resistance was testedand found excellent with little loss of strength properties. Thisprocedure has been used commercially on approximately 1,000,000 yards offabric with remarkable uniformity of low damage from retained chlorine.

Example II A condensation product of acrolein, urea and formaldehyde wasprepared generally in accordance with the procedure of US. Patent2,600,780 issued to Franz Kohler June 17, 1952, using the followingingredients:

Parts Formaldehyde (37%) 1525 Urea 425 Acrolein 150 Water 220 Aceticacid 4 One part by weight of this product (45% solids) was mixed withthree par-ts by weight of 1,3 dimethylol-5-ethyl-tetrahydro-2(1)-s-triazone (50% solids).

A plain woven bleached mercerized and soured 100% cotton gingham fabricrunning about 4 /2 yards per pound was impregnated with about 65% of itsown weight of an aqueous solution containing 1% of a 23% solution ofmonoethanolamine hydrochloride catalyst and 15% of the above describedmixture. The thus impregnated fabric was dried at 200 F. and cured at300 F. for 70 seconds.

The wrinkle resistance of the treated fabric was found to be high andthe strength properties of the fabric were excellent. The damage fromretained chlorine was uniformly low contrary to normal expectations.

Exmnple III A plain woven bleached mercerized and soured 100% cottongingham fabric running about 4 /2 yards per pound was impregnated withabout 65% of its own weight of an aqueous solution containing about 1%of the 50% solution of monoethanolamine hydrochloride catalyst, andabout 15% of a mixture containing one part of a 50% solids solution ofdimethylol ethylene urea and one part of 1,3 dimethylol 5 ethyltetrahydro-2(1)-s-triaz0ne (50% solids).

The thus impregnated fabric was dried at 200 F. and cured for 70 secondsat 320 F. The treated fabric had excellent wrinkle resistance, strengthproperties and resistance to damage from retained chlorine. Thisprocedure has been used commercially on both plaids and all whites withuniformly good results.

Thus it will be seen that the gist of the present invention is thedepression of the damage caused by retained chlorine in resin treatedfabrics by the addition of the specified triazones to the fabricimpregnating solutions.

It will be obvious that the depressants of this invention are usefulwith mixtures of highly chlorine retentive resins as well as individualresins. This is illustrated in the following example:

Example IV The procedure of Example I was repeated using, in place ofthe final resin forming mixture alone, a mixture of 193 parts of thatproduct and 307 parts of a 50% solution of dimethylol ethylene urea. Theresults of Example I were generally duplicated in an extended test ofcommercial production.

Good results were obtained with other1,3-dimethyloltetrahydro-2(1)-s-triazones including the unsubstitutedproduct, the 5 methyl product, the 5 propyl, the 5 isopropyl, the 5ethanol and the 5 propanol. These results vary somewhat from product toproduct but the general pattern of results is always very similar.

Example V A mixture of dimethylol urea and 1,3 dimethylol-5-ethyl-tetrahydro-2(1)-s-triazone in a mol ratio of about 1 to 1 wasprepared using the following ingredients:

Portion A: Parts Urea formaldehyde concentrate- (Allied Chemical) (60%formaldehyde, 25% urea and the balance water) 1000 Urea 40Monoethylamine (71%) 320 Portion B:

Urea formaldehyde concentrate-85 (Allied Chemical) 540 Urea 185 The ureaformaldehyde concentrate-85 and urea of portion A were mixed. Themonoethylamine solution was added slowly, keeping the temperature 'belowF. by cooling. This mixture was heated to F. and held at thattemperature for one hour and 20 minutes, after which it was cooledslightly and a previously prepared mixture of the components of portionB were added. This mixture was heated to about 160 F. for 15 minutes,after which it was cooled to about 120 F.l30 F. and then adjusted to pH5 plus or minus 0.1. At this stage the intermediate product was amixture of dimethylol urea and dimethylol triazone ready for thepre-polymerization step.

Pre-polymerization was carried out as follows: This intermediate productwas then heated to 160 F. for one and one-half hours after which it wascooled and adjusted to pH 5-pI-I 5.5. The final product was a viscousclear syrup Water soluble in any and all proportions. In other runs ofthis experiment the last heating cycle (on the acid side) was varied toobtain different degrees of stiffening properties on textile fabrics. Itwas found that the longer the heating cycle, the greater the degree ofpolymerization and accordingly the greater the stiffening effect of theproduct on a fabric treated therewith. Likewise, other experimentsvarying the pH of the final heating cycle and the time and temperatureof the heating cycle also adjusted the stiffening properties of thefinal product in that a lower pH, a higher heating temperature, or alonger heating time would all increase the degree of polymerization andthus the stiffening of the final product.

The product prepared in accordance with the specified conditions of theabove example was still water soluble in any and all proportions aftermore than five months storage at room temperature.

Example VI A pre-polymerized product containing the reaction product ofdimethylol urea and 1,3, dimethylol-S-ethyl- '13 2(1)-s-tr'iazone in amolar ration of about 1 to l was prepared using the followingingredients:

. Parts Urea formaldehyde concentrate-85 (Allied Chemical) 1000 Urea 146Monoethylarnine (71% 208 The urea formaldehyde concentrate-85 and ureawere mixed and the monoethylamine was added slowly with cooling, keepingthe temperature below 140 F. This mixture was then heated to 160 F. forone and one-half hours, after which it was cooled to 130 F. and adjustedto pH 5.5.

This mixture of urea formaldehyde and triazone formaldehyde was thenpro-polymerized by being heated to 160 F.-1 65 F. for one hour. Thefinal product was cooled and adjusted to pH 5. This product was alsosimilar in appearance to the product of Example V, but it did notstiffen textile fabrics quite as much as that product. This product wasstored at room temperature for five months and at the end of that timeit was still water soluble in any and all proportions.

Perhaps the most unexpected result of the work forming the basis of thethree examples above was the fact that the final products had a shelflife well above and beyond that of comparable products of the prior art.This is true not only of the specific triazone formaldehyde shown in theexamples but also extends to the combinations of urea formaldehyde andthe other triazone formaldehydes defined above.

The stability of the final product is somewhat responsive to its storagepH. It is almost infinitely stable when neutral or slightly alkaline. Ofcourse, as the finished pH is lowered, there is a tendency forpolymerization to continue, but for practical purposes this isnegligible at no lower than pH 5. It is preferable to store the productin a slightly acid condition as alkaline products require excessiveamounts of catalyst in application to textile fabrics.

Example VII The products of Examples V and VII were compared byapplication of each to a plain weave cotton gingham (about 4%. yards perpound) under identical conditions. The formula used in each instance wasas follows:

% of the product of one of the above examples,

1% of a 23% solution of monoethanolamine, hydrochloride as a catalyst,

Balance water.

The fabric was impregnated with about 70% of its own weight of theabovesolution, dried to about 10% moisture content and cured at about360 F. for seventy seconds in each instance. Each of the treated fabricshad a stiff and firm hand, a relatively high degree of wrinkleresistance, very low damage from retained chlorine and no tendency toyellow on treatment with hot Clorox. A comparison of the properties ofthe treated fabrics may be seen in Table I below:

linings of shirt collars Was treated with the following formula:

30% of the product of Example V,

4% corn starch (Hawk),

1% polyvinyl alcohol (Elvanol 72-60),

1% of a 23% solution of monoethanolamine hydrochloride as catalyst,

Balance water.

The fabric was impregnated with about 70% of its own weight of the abovesolution, dried to about 10% moisture and cured for seventy seconds at360 F. Upon testing, this product was found to have an exceptionallyhigh wrinkle resistance; namely, 3.6 x 3.6, according to the TBL testmethod. The fabric also had an exceptionally stiff hand which waspermanent to washing. It also possesses the other desirable propertiesof the products of Example VII.

Example IX A plain weave rayon fabric (about 3 /2 yards per pound) wastreated using the following formula:

15% of a product containing the product of Example I,

2% of a 23% solution of monoethanolamine hydrochloride,

0.5% of softener (Ahcovel G),

Balance water.

The prepared rayon was impregnated with about of its own weight of theabove solution, framed and dried to about 8% moisture at a temperatureof about 230 F. to 240 F. This fabric was then cured at 310 F. for sixminutes, after which it was washed and framed according to the usualpractice of the art. The thus treated fabric had an exceptionally firmhand similar to that of some finished linen fabrics. It had a TBLwrinkle resistance of 3.0 x 2.8, a trapezoid filling tear of 4.3 pounds,no damage from retained chlorine, no Clorox yellowing and ex tremelygood dimensional stability. Dimensional stability was tested by AATCCstandard test method 14-53 and after ten such washes the warp shrinkagewas only 1.11% and the filling showed a gain of 1.39%.

The products of Examples V, and VI were also used as supplemental handbuilders in fmishing rayon with other resin forming materialscommercially used to provide dimensional stability and Wrinkleresistance, including acrolein-urea-formaldehyde resins and ureaformaldehyde resins which had not been pre-polymerized. The productswere exceptionally satisfactory in such uses.

With the combined properties of stiffening, wrinkle resistanceproducing, dimensional stabilization and low dam-age from retainedchlorine, in addition to the good stability of the product, this textiletreating product is distinctly different from the stiffening resinsknown in the prior art.

It should be noted that if the degree of polymerization is too great,the shelf life will be adversely effected, although the stiffeningproperties are increased and the assurance of low damage from retainedchlorine is increased. There is a very wide range of satisfactory resinAfter ten commercial white washes the properties of forming materialswhich may be obtained in accordance the fabric had not changedsignificantly.

Example VIII A plain loose weave construction of cotton fabric with thispart of the invention to meet the needs of specific uses.

Example X A resin-forming material suitable for treating textiles (about4 yards per pound) intended to be used for inner was prepared by heating0.37 mol of hexamethylene di- 15 amine with one mol of urea and fourmols of formaldehyde as Formalin under alkaline conditions in water atabout 180 F. A white solid product of undetermined constitution wasfound immediately. Heating at about 16 divided into two portions, one ofwhich was cured for 70 seconds at 155 C. and the other of which wascured for 70 seconds at 180 C. The results of this example may betabulated as follows:

Curing Wrinkle Chlorine Resin-Forming Material Tcmper- Resistance TearTensile Retention Reflectance ntnre (TBL) Strength Strength (Percent 1110. Loss) P:oduct of Example X" 155 3.0 x 3. 2.15 30. 17 83.5 Product ofExample X. 150 3.1 x 3.1 1.95 27. 5 5 81. 4 Product of Example XI. 1553.1 x 3.1 1.90 27. 7 11 84. 2 Product of Example X1... 180 3.3 x 3. 31.70 24. 7 3 81. 5

1 Untreated.

180 F. was continued with stirring and the final product was formedafter about seven hours. It will be seen that the final product was amixture of dimethylol urea and triazone formaldehyde in a theoreticalmolar ratio of about 1 to 2.85 respectively. The particular triazone hasthe following formula:

The amount of water in the product was adjusted to bring the solidscontent to about 50% and the pH was adjusted to pH 5 with muriatic acid.The final product is a clear solution. If any solids remain, the productshould be filtered.

Example XI A second product was prepared in the same manner with theexception that 0.25 mol of hexamethylene diamine was used in place ofthe 0.37 mol of the previous example. It will be seen that this changesthe ultimate theoretical mol ratio to one to one.

Example XII A resin forming material suitable for treating textiles wasprepared by heating 0.37 mol of hexamethylene diamine with one mol ofurea and four mols of formaldehyde as Formalin at pH 6.06.9 in water atabout 180 F.

A mixture of the reactants was formed in water without adjusting the pH.A white solid product of undetermined constitution was formedimmediately. This mixture was heated at about 180 F. for about 30minutes, after which the pH was adjusted to about pH 6.0 to 6.9 andheating was continued at the same temperature for another 1 /2 hours, toform the final product. This product was finished off as in Example Xand the product was almost identical in appearance and reactivity to theproduct of Example XI.

Example XIII A resin forming material suitable for treating textiles wasprepared by heating 0.50 mol of hexamethylene diamine with one mol ofurea and four mols of formaldehyde reacted under the conditionsspecified in Example XII. The final product was a clear solution havingthe general appearance of the products of Examples X and XI.

Example XIV A series of comparative experiments were run to determinethe effectiveness of the products produced in Examples X and XI astextile treating materials for the production of high wrinkle resistancewith low damage from retained chlorine. In these experiments, a cottonAfter five severe cotton washes, these same samples still had almostidentical physical properties, the only measured changes being in thenature of expected experimental error.

Example XV An aqueous solution was prepared containing 5% of the productof Example X111 (50% solids), 10% of a 50% solution of dimethylolethylene urea and 1% of 23% solution of monoethanolamine hydrochlorideas catalyst. A cotton gingham fabric was impregnated with about 75% ofits own weight of the above solution. A second sample of the same fabricwas impregnated with a solution prepared the same way except that theproduct of Example XIII was omitted. Both fabric samples were dried andcured at 170 C. for 70 seconds. The fabric containing the product ofExample XIII was tested and found to have good wrinkle resistance, tearstrength, tensile strength and low damage from retained chlorine. Thesimilarly processed fabric without the product of Example XIII also hadgood wrinkle resistance, tear strength and tensile strength, but wasfound to have a considerably higher loss of strength from retainedchlorine, with losses ranging up to 50%. On repeated laundering andretesting the good sample retained its'resistance to chlorine damagewhile the simple without the product of Example XIII becameprogressively more susceptible to chlorine damage.

Triazone formaldehydes similar to those described in Examples X-XV havebeen prepared and found satisfactory by replacing hexamethylene diaminewith other aliphatic diamines including pentamethylene diamine andethylene diamine.

Example XVI A triazone formaldehyde corresponding to the formula:

Fal s was prepared by adding 25 grams of methyl urea to 61 grams of 37%formaldehyde, adjusting the pH to about pH 89 and heating to F. forabout 5 minutes and cooling to form as an intermediate, dimethylolmethyl urea. This product was then reacted with 21 grams of 71% ethylamine by heating at 160 F. to F. for two hours to form a triazone.Thirty and one-half grams of 37% formaldehyde were added to the thusformed product and the mixture was heated to 160 F.170 F. for tenminutes to form the triazone formaldehyde. Upon cooling, the product wasadjusted to pH 5.0.

An aqueous solution containing 10% of the thus formed product, 5%(solids basis) dimethylol urea, and 0.5% zinc nitrate was prepared. Acotton fabric was then impregnated with about 75% of its weight of theaqueous solution, dried, and baked at 170 C. for 70 seconds.

:1 7 On testing the fabric was found to have lowdamage from retainedchlorine and good wrinkle resistance.

Example XVII A triazone formaldehyde corresponding to the formula: oa s(F2115 l, l was prepared by refluxing for 3-4 hours, 2 mols of urea (360grams) with one mol of ethylene diamine (189 grams of 91% product). Thethus formed intermediate was crystallized with 95% ethanol and found tobe ethylene diurea of the formula:

To this product 4 mols (324 grams) of 37% formaldehyde and 2 mols (126.6grams) of 71% ethylamine were added. The mixture was heated to 160-170F. for 1 /2 hours to form the triazone. Two mols (162 grams) of 37%formaldehyde were added to the triazone while the temperature was keptat 160-170 F. for five minutes to form the triazone formaldehyde. Thefinal product was cooled and adjusted to pH 5.0-5.5.

A cotton fabric was then impregnated with about 75% of its weight of anaqueous solution containing 0.5% zinc nitrate, of the product preparedabove in this example and 5% (solids 'basis) urea formaldehyde. Thefabric was then dried and baked at 170 C. for 70 seconds. On testing theproduct was found to have good Wrinkle resistance and lower damage fromretained chlorine than the product of Example XVII.

Similar satisfactory triazone formaldehydes were prepared by usingequivalent molar quantities of hexamethylene diamine and pentamet'hylenediamine in place of ethylene diamine.

Many of the examples of the invention use amine hydrochloride catalystswhich are satisfactory. However, minimum discoloration is obtained withmetal salt catalysts such as magnesium chloride or zinc nitrate.

Thus, it will be seen that the present invention is primarilycharacterized by the depression of the damage caused by retainedchlorine in resin treated fabrics by the addition of the triazoneformaldehyde depressants of this invention. Improvements of the basicinvention include especially the pre-polymerized mixtures of urea formaldehyde and triazone formaldehyde which are characterized by unexpectedstability. A second important improvement is the process of preparingespecially efficient mixtures of urea formaldehyde and triazoneformaldehyde by reacting urea and formaldehyde with a primary alkylamine in a quantity providing less than an equimolar quantity of primaryamine groups.

What is claimed is:

1. In the process of treating cellulose textile fabrics to producewrinkle resistance wherein said fabric is impregnated with an aqueoussolution containing an acid catalyst and a resin forming material, thefabric is dried and the resin forming material is cured, thatimprovement which comprises using as the resin forming material twocomponents including a first component having a high wrinkle resistancevalue and a high coeificient of chlorine damage and a second componentbeing a chlorine damage depressant, the quantity of the two componentsbeing sufficient to produce high wrinkle resistance and said quantitybeing of from about 5% to 40% by weight of said aqueous solution, saidfirst component being a watersoluble urea-formaldehyde condensateselected from the group consisting of urea formaldehyde, acroleinmodified urea formaldehyde, and tetramethylol acetylene diurea and saidsecond component being a triazone formaldehyde having the formula:

wherein n is a number from 2 to 6, R is selected from the groupconsisting of hydrogen, methylol, methoxymethyl, an alkyl group havingfrom 1 to 4 carbon atoms and the triazone group:

and wherein said second component contains at least one group selectedfrom the group consisting of methylol and methoxymethyl and wherein saidsecond component has no more than two triazone rings, and the molarratio of said components being regulated to substantially depress thecoeflicient of chlorine retention of said first component whilemaintaining high wrinkle resistance, said molar ratio when said firstcomponent is urea formaldehyde being within the range of from about 1 to6.3 mols of said second component for each mol of combined urea in saidurea formaldehyde, said molar ratio when said first component isacrolein modified u-rea formaldehyde being within the range of fromabout 0.5 to 10 mols of said second component for each mol of combinedurea in said acrolein modified urea formaldehyde, and said molar ratiowhen said first component is tetramethylol acetylene diurea being withinthe range of from about 2 to 10 mols of said second component for eachmol of said tetramethylol acetylene diurea.

2. The process as set forth in claim 1 wherein the cellulose textilefabric contains cotton fibers, said first component isurea-formaldehyde, said second component isl,3-dimethylol-S-ethyI-tetrahydro-2( l )-s-triazone and the molar ratiois about 1 to 6.3 of urea formaldehyde to said second component,respectively.

3. The process as set forth in claim 1 wherein said second component is:

4. The process as set forth in claim 1 wherein said second component is:

CgH 1% C I: CHa

5. The process as set forth in claim 1 wherein said first component isacrolein modified urea formaldehyde, the cellulose textile fabriccontains cotton fibers and said second component is1,3-dimethylol-S-ethyl-tetrahydro- 2( 1 )-s-triazone.

6. The process as set forth in claim 1 wherein the cellulose textilefabric is cotton and said first component is tetramethylol acetylenediurea and said second component is a 1,3-dimethylol monotriazone.

7. A new composition of matter for treating textiles comprising a resinforming material including a first component having a high wrinkleresistance value and a high coefficient of chlorine damage and a secondcomponent which is a chlorine damage depressant, said first componentbeing a water-soluble urea-formaldehyde condensate selected from thegroup consisting of urea formaldehyde, acrolein modified ureaformaldehyde, and tetramethylol acetylene diurea and said secondcomponent being a triazone formaldehyde having the formula:

wherein R is selected from the group consisting of hydrogen, methylol,and methoxymethyl, R is selected from the group consisting of hydrogenand an alkyl group having from 1 to 3 carbon atoms, R is selected fromthe group consisting of hydrogen, methoxymethyl, an alkanol group havingfrom 1 to 4 carbon atoms, an alkyl group having from 1 to 4 carbon atomsand the triazone group:

i /CHN 2)X.N =O

E R1 R4 wherein n is a number from 2 to 6, R is selected from the groupconsisting of hydrogen, methylol, methoxymethyl, an alkyl group havingfrom 1 to 4 carbon atoms and the triazone group:

(C 2) u N and wherein said second component contains at least one groupselected from the group consisting of methylol and methoxymethyl andwherein said second component has no more than two triazone rings, andthe molar ratio of said components being regulated to substantiallydepress the coefiicient of chlorine retention of said first componentwhile maintaining high wrinkle resistance, said molar ratio when saidfirst component is urea formaldehyde being within the range of fromabout 1 to 6.3 mols of said second component for each mol of combinedurea in said urea formaldehyde, said molar ratio when said firstcomponent is acrolein modified urea formaldehyde being within the rangeof from about 0.5 to 10 mols of said second component for each mol ofcombined urea in said acrolein modified urea formaldehyde, and saidmolar ratio when said first component is tetramethylol acetylene diureabeing within the range of from about 2 to 10 mols of said secondcomponent for each mol of said tetramethylol acetylene diurea.

8. A composition as set forth in claim 7 in which said first componentis urea formaldehyde.

9. A composition as set forth in claim 8 wherein said second componentis 1,3-dimethylol-S-ethyl-tetrahydro- 2(1)-s-triazone and said molarratio is about 1 to about 6.3.

10. A composition of matter as set forth in claim 7 wherein said firstcomponent is acrolein modified urea formaldehyde and said secondcomponent is a 1,3-dimethylol monotriazone.

11. A composition as set forth in claim 7 wherein said first componentis tetramethylol acetylene diurea and said second component is a1,3-dimethylol monotriazone.

12. A textile fabric characterized by low damage from retained chlorineand high wrinkle resistance, said fabric being formed predominantly ofcellulose fibers impregnated with from about 5% to 20% of their weightof a composition of matter comprising a resin comprising a firstcomponent providing high wrinkle resistance and a second component whichis a chlorine damage depressant, said first component being awater-soluble urea-formaldehyde condensate selected from the groupconsisting of urea formaldehyde, acrolein modified urea formaldehyde,and tetramethylol acetylene diurea and said second component being atriazone formaldehyde having the formula:

Ra I

wherein R is selected from the group consisting of hydrogen, methylol,and methoxymethyl, R is selected from the group consisting of hydrogenand an alkyl group having from 1 to 3 carbon atoms, R is selected fromthe group consisting of hydrogen, methoxymethyl, an alkanol group havingfrom 1 to 4 carbon atoms, an alkyl group having from 1 to 4 carbon atomsand the triazone group:

CHN a)uN o=0 oH-N wherein n is a number from 2 to 6, R is selected fromthe group consisting of hydrogen, methylol, methoxymethyl, an alkylgroup having from 1 to 4 carbon atoms and the triazone group:

and wherein said second component contains at least one group selectedfrom the group consisting of methylol and methoxymethyl and wherein saidsecond component has no more than two triazone rings, and the molarratio of said components being regulated to substantially depress thecoefficient of chlorine retention of said first component whilemaintaining high wrinkle resistance, said molar ratio when said firstcomponent is urea formaldehyde being within the range of from about 1 to6.3 mols of said second component for each mol of combined urea in saidurea formaldehyde, said molar ratio when said first component isacrolein modified urea formaldehyde being within the range of from about0.5 to 10 mols of said second component for each mol of combined urea insaid acrolein modified urea formaldehyde, and said molar ratio when saidfirst component is tetramethylol acetylene diu-rea being within therange of from about 2 to 10 mols of said second component for each molof said tetramethylol acetylene diurea.

13. A fabric as set forth in claim 12 wherein said fabric containscotton fibers, said first component is urea formaldehyde and. saidsecond component is a 1,3-dimethylol monotriazone, and the molar ratioof said components is about 1 to 6.3 of urea formaldehyde to saidtriazone, respectively.

14. A process for treating cellulose textiles comprising applyingthereto an aqueous solution of a curable mixture of (a) a water solubleurea-formaldehyde condensate and (b) a compound of the formula:

wherein R is an alkyl group having 1-4 carbon atoms, the mole ratio of(b) to (a) being from about 1:1 to about 3:1, based on the amount ofcombined urea in said condensate (a) and thereafter heating to dry andcure the resin.

15. A composition as set forth in claim 8 wherein said second componentis:

16. A fabric as set forth in claim 12 wherein said first component isurea formaldehyde and said second component is:

17. A process for treating cellulosic textiles comprising applyingthereto an aqueous solution of a curable mixture of (a) a water-solubleurea-formaldehyde condensate and (b) a compound of the formula:

NCHrOR' wherein R is a member of the class consisting of hydrogen,methoxymethyl, an alkanol group having 1 to 4 carbon atoms and an alkylgroup having 1 to 4 carbon atoms, R is a member of the class consistingof hydrogen and methyl, the mol ratio of (b) to (a) being about 1:10 toabout 10:1, based on the amount of combined urea in said condensate (a),drying the textile and curing the resin.

18. Process as claimed in claim 17 wherein said compound is 1,3dimethylol -(2-hydroxyethyl)tetrahydro- 2(1)-triazone.

19. Process as claimed in claim 17 wherein said watersolubleurea-formaldehyde condensate is acyclic.

IIICHzO R wherein R is a member of the class consisting of hydrogen,methoxymethyl, an alkanol group having 1 to 4 carbon atoms and an alkylgroup having 1 to 4 carbon atoms, R is a member of the class consistingof hydrogen and methyl, and the mol ratio of (b) to (a) is from about1:1 to about 10:1.

21. New composition as claimed in claim 20 wherein saidurea-formaldehyde condensate consists of a methylol urea.

22. New composition as claimed in claim 21 wherein saidurea-formaldehyde condensate is dimethylol urea.

23. New composition as claimed in claim 20 wherein saidurea-formaldehyde condensate is acyclic.

24. New composition as claimed in claim 20 wherein said compound is1,3-dimethylol-5-(2-hydroxyethyl)tetrahydro-2( 1 -triazone.

25. New composition as claimed in claim 7 wherein said compound is1,3-dimethylol-5-(2-hydroxyethyl)tetrahydro-2( 1 triazone.

26. Process as claimed in claim 1 wherein the impregnated fabric isheated to dry the fabric and cure the resin in one operation.

27. Process of making an aqueous solution containing a bis triazone ofthe formula References Cited UNITED STATES PATENTS 2,370,839 3/1945Burke et al. 260-675 2,373,135 4/1945 Maxwell 260-72 2,373,136 4/ 1945Hoover et al. 260-675 2,641,584 6/1953 Martone 260-173 2,690,404 9/1954Spangler et a1. 117-139.4 2,755,198 7/1956 Stewart 117-1394 2,804,402 8/1957 Williams 260-849 2,826,500 3/1958 Keim 260-70 X 2,884,407 4/ 1959Keim 260-70 2,901,463 8/1959 Hurwitz 260-70 MURRAY TILLMAN, PrimaryExaminer.

MILTON STERMAN, R. D. NEVTUS, Examiners.

G. B. DUNAWAY, T. L. TULLY, W. D. MARTIN,

I. C. BLEUTGE, Assistant Examiners.

1. IN THE PROCESS OF TREATING CELLULOSE TEXTILE FABRICS TO PRODUCEWRINKLE RESISTANCE WHEREIN SAID FABRIC IS IMPREGNATED WITH AN AQUEOUSSOLUTION CONTAINING AN ACID CATALYST AND A RESIN FORMING MATERIAL, THEFABRIC IS DRIED AND THE RESIN FORMING MATERIAL IS CURED, THATIMPROVEMENT WHICH COMPRISES USING AS THE RESIN FORMING MATERIAL TWOCOMPONENTS INCLUDING A FIRST COMPONENT HAVING A HIGH WRINKLE RESISTANCEVALUE AND A HIGH COEFFICIENT OF CHLORINE DAMAGE AND A SECOND COMPONENTBEING A CHLORINE DAMAGE DEPRESSANT, THE QUANTITY OF THE TWO COMPONENTSBEING SUFFICIENT TO PRODUCE HIGH WRINKLE RESISTANCE AND SAID QUANTITYBEING OF FROM ABOUT 5% TO 40% BY WEIGHT OF SAID AQUEOUS SOLUTION, SAIDFIRST COMPONENT BEING A WATERSOLUBLE UREA-FORMALDEHYDE CONDENSATESELECTED FROM THE GROUP CONSISTING OF UREA FORMALDEHYDE, ACROLEINMODIFIED UREA FORMALDEHYDE, AND TETRAMETHYLOL ACETYLENE DIUREA AND SAIDSECOND COMPONENT BEING A TRIAZONE FORMALDEHYDE HAVING THE FORMULA: